Polymerizable compositions including a phthalonitrile resin and a polyoxometalate, articles, and methods

Abstract

The present disclosure provides a polymerizable composition. The polymerizable composition includes a phthalonitrile resin, a curative, and a polyoxometalate of Formula I: H n [XM 12 O 40 ] (I). In Formula (I), M is W or Mo, n is 1 to 6, and X is a heteroatom selected from P, Si, S, Ge, As, Te, or Se. The present disclosure also provides an article. The article includes a polymerization product of the polymerizable composition. Additionally, a method is provided. The method includes mixing a polyoxometalate of Formula I with at least one of a curative or phthalonitrile resin and mixing at least a portion of the curative with at least a portion of the phthalonitrile, thereby forming a polymerizable composition. The method further comprises subjecting the polymerizable composition to a temperature of 180° C. to 250° C., to form an at least partially polymerized article and subjecting the at least partially polymerized article to a temperature of 300° C. to 350° C. to complete polymerization of the article.

What is claimed is: 
     
       1. A polymerizable composition comprising:
 a) a phthalonitrile resin; 
 b) a polyoxometalate of Formula I: H n [XM 12 O 40 ] (I), 
 wherein M is W or Mo, n is 1 to 6, and X is a heteroatom selected from P, Si, S, Ge, As, Te, or Se; and 
 c) a curative. 
 
     
     
       2. The polymerizable composition of  claim 1 , wherein in Formula I, M is W. 
     
     
       3. The polymerizable composition of  claim 1 , wherein the polyoxometalate is H 3 [P(W 3 O 10 ) 4 ] or H 4 [Si(W 3 O 10 ) 4 ]. 
     
     
       4. The polymerizable composition of  claim 1 , wherein in Formula I, M is Mo. 
     
     
       5. The polymerizable composition of  claim 1 , wherein the polyoxometalate is H 3 [P(Mo 3 O 10 ) 4 ]. 
     
     
       6. The polymerizable composition of  claim 1 , wherein the phthalonitrile resin comprises at least one of bis(3,4-dicyanophenyl) ether of bisphenol M, bis(3,4-dicyanophenyl) ether of bisphenol T, or bis(3,4-dicyanophenyl) ether of resorcinol. 
     
     
       7. The polymerizable composition of  claim 1 , wherein the curative comprises an aniline functional phthalonitrile. 
     
     
       8. The polymerizable composition of  claim 1 , wherein the curative comprises a dianiline functionality. 
     
     
       9. The polymerizable composition of  claim 1 , wherein the curative comprises a phenol functionality. 
     
     
       10. The polymerizable composition of  claim 1 , wherein the curative comprises a phenol functional phthalonitrile. 
     
     
       11. The polymerizable composition of  claim 1 , further comprising at least one filler comprising at least one of reinforcing continuous fibers or reinforcing discontinuous fibers, a fabric, a nanofiller, or a microfiller. 
     
     
       12. An article comprising a polymerization product of the polymerizable composition of  claim 1 . 
     
     
       13. The article of  claim 12 , exhibiting a tensile ultimate strength of 75 megapascals (MPa) or greater. 
     
     
       14. The article of  claim 12 , exhibiting a tensile ultimate strain of 3% or greater. 
     
     
       15. A method of making an article, the method comprising:
 a) mixing a polyoxometalate with at least one of a curative or phthalonitrile resin,
 wherein the polyoxometalate is of Formula I: H n [XM 12 O 40 ] (I), 
 wherein M is W or Mo, n is 1 to 6, and X is a heteroatom selected from P, Si, S, Ge, As, Te, or Se; 
 
 b) mixing at least a portion of the curative with at least a portion of the phthalonitrile, thereby forming a polymerizable composition comprising the phthalonitrile resin, the curative, and the polyoxometalate; 
 c) subjecting the polymerizable composition to a temperature of 180° C. to 250° C., to form an at least partially polymerized article; and 
 d) subjecting the at least partially polymerized article to a temperature of 300° C. to 350° C. to complete polymerization of the article. 
 
     
     
       16. The method of  claim 15 , wherein the polyoxometalate is obtained by dehydrating a polyoxometalate hydrate. 
     
     
       17. The method of  claim 16 , wherein the polyoxometalate is dehydrated during step a) by mixing the polyoxometalate hydrate with a solvent to form a polyoxometalate composition, mixing the phthalonitrile with a solvent at elevated temperature to form a phthalonitrile composition, combining the polyoxometalate composition with the phthalonitrile composition, and removing the solvent. 
     
     
       18. The method of  claim 15 , wherein the polyoxometalate is mixed with the curative by mixing the polyoxometalate with a solvent to form a polyoxometalate composition, mixing the curative with a solvent to form a curative composition, combining the polyoxometalate composition with the curative composition, and removing the solvent.